Physical Sciences and Mathematics Commons^™

Potentially Massive And Global Non-Pyrogenic Production Of Condensed "Black" Carbon Through Biomass Oxidation, Aleksandar I. Goranov, Hongmei Chen, Jianshu Duan, Satish C. B. Myneni, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

With the increased occurrences of wildfires worldwide, there has been an increase in scientific interest surrounding the chemistry of fire-derived "black" carbon (BC). Traditionally, wildfire research has assumed that condensed aromatic carbon (ConAC) is exclusively produced via combustion, and thus, ConAC is equated to BC. However, the lack of correlations between ConAC in soils or rivers and wildfire history suggests that ConAC may be produced non-pyrogenically. Here, we show quantitative evidence that this occurs during the oxidation of biomass with environmentally ubiquitous hydroxyl radicals. Pine wood boards exposed to iron nails and natural weather conditions for 12 years yielded a …

Organic Matter Content And Grain Size Analysis In Seagrass Sediments, Adriana Amrhein, Rip Hale

College of Sciences Posters

Anthropogenic stresses including increased water temperatures, decreased water quality, sea level rise, ocean acidification and sediment biogeochemical processes have caused a significant loss in seagrass meadow acreage. Seagrass meadows provide coastal protection from storms and recently have been emphasized for their importance in sequestering and storing “Blue Carbon” from the atmosphere and ocean. Seagrass meadows can trap this blue carbon in their sediment as organic carbon, and it can be stored for hundreds to thousands of years. Restoration efforts of seagrass meadows in the Virginia coast started in the 1990s and effects of increasing seagrass density can be observed in …

Dust Deposition To The Bermuda Region: A Comparison Of Estimates Using Seasonally-Resolved Measurements Of Aluminum In Water-Column, Aerosol, And Rain Samples, Tara Williams, Peter Sedwick, Bettina Sohst, Joe Resing, Kristen Buck, Salvatore Caprara, Rod Johnson, Dan Ohnemus, Ben Twining, Alessandro Tagliabue

College of Sciences Posters

Dust deposition is a major source of bioactive trace elements to the surface ocean, yet this flux remains difficult to constrain. Previously, time-averaged dust flux has been estimated using surface ocean dissolved aluminum (DAl) concentrations, assumed values for aerosol aluminum solubility (%Al_S), and the residence time of DAl in the surface mixed layer (SML). We apply this method to estimate dust deposition in the Bermuda Atlantic Time-series Study (BATS) region using water-column DAl data from cruises in 2019, which is compared with direct flux estimates from contemporaneous measurements of aluminum in aerosols and rain collected on Bermuda. Seasonal …

Revisiting 228Th As A Tool For Determining Sedimentation And Mass Accumulation Rates, Joseph J. Tamborski, Pinghe Cai, Meagan Eagle, Paul Henderson, Matthew A. Charette

OES Faculty Publications

The use of ²²⁸Th has seen limited application for determining sedimentation and mass accumulation rates in coastal and marine environments. Recent analytical advances have enabled rapid, precise measurements of particle-bound ²²⁸Th using a radium delayed coincidence counting system (RaDeCC). Herein we review the ²²⁸Th cycle in the marine environment and revisit the historical use of ²²⁸Th as a tracer for determining sediment vertical accretion and mass accumulation rates in light of new measurement techniques. Case studies comparing accumulation rates from ²²⁸Th and ²¹⁰Pb are presented for a micro-tidal salt marsh and a marginal sea …

Reconstructing Surface Water Carbonate Ion Concentration Changes In The Eastern Equatorial Pacific Across Glacial Transitions, Lenzie Gail Ward

OES Theses and Dissertations

Today, the eastern equatorial Pacific (EEP) plays a critical role in the global CO₂ budget as a major source of CO₂ to the atmosphere, but recent studies suggest the region may shift to a sink for atmospheric CO₂ under different climate states. Here, I focus on two transitional periods, the last deglaciation (25 kyr to present) and last glaciation (the Marine Isotope Stage (MIS) 5a-4 transition, 96 to 60 kyr), to investigate how the carbon system in the EEP responds to major climate changes. I measured B/Ca ratios in the planktic foraminifera Globigerina bulloides from core MV1014-17JC …

Sodium-Calcium Ratios In The Planktic Foraminifera Trilobatus Sacculifer As A Proxy For Sea Surface Salinity, Colton Steele Watkins

OES Theses and Dissertations

Recent culture and field studies have found a significant positive correlation between seawater salinity and the incorporation of sodium into foraminiferal calcite, suggesting a potential new proxy for reconstructing past changes in sea surface salinity (SSS) (Mezger et al., 2016 and Bertlich et al., 2018). In order to test the applicability of this new proxy in an open-ocean setting, Na/Ca ratios in the planktic foraminifera Trilobatus sacculifer (T. sacculifer Na/Ca) were measured from a suite of sediment core tops spanning a natural salinity gradient from the North Atlantic subtropical gyre to the South Atlantic subtropical gyre. Initial results from …

Structural Characterization Of Organic Matter In Oil Shales Using Multiple Nuclear Magnetic Resonance Spectroscopic Techniques, Wenying Chu

Chemistry & Biochemistry Theses & Dissertations

Oil shale is a promising source of hydrocarbon fuel that is distributed throughout the world. The petroleum generating potential of oil shale is related to the molecular structure of the organic matter in source rock. The major fraction of organic matter of oil shale is termed kerogen, and due to its insolubility in organic solvents, ¹³C solid-state nuclear magnetic resonance (NMR) spectroscopy is one of the best ways to directly measure the insoluble organic matter without changing its chemical structures. This dissertation investigated oil shale samples using advanced solid-state ¹³C NMR spectroscopy techniques and high resolution magic angle …

An Introduction To “Microbial Biogeochemistry: A Special Issue Of Aquatic Geochemistry Honoring Mark Hines”, W. Berry Lyons, David J. Burdige

OES Faculty Publications

(First paragraph) This issue of Aquatic Geochemistry is dedicated to the memory of Dr. Mark E. Hines (Fig. 1) and his contributions to the fields of microbial biogeochemistry and aquatic geochemistry. Mark passed away in March of 2018, and through his career as a researcher, teacher, mentor, colleague, and university administrator, he greatly influenced the lives of all around him. We hope that this volume will serve not only as a memory of Mark, but also as a way to recognize his significant influences and major contributions in the fields of carbon, sulfur, and trace element biogeochemistry.

Marine Carbonyl Sulfide (Ocs) And Carbon Disulfide (Cs2): A Compilation Of Measurements In Seawater And The Marine Boundary Layer, Sinikka T. Lennartz, Christa A. Marandino, Marc Von Hobe, Meinrat O. Andreae, Kazushi Aranami, Elliot Atlas, Max Berkelhammer, Heinz Bingemer, Dennis Booge, Gregory A. Cutter, Pau Cortes, Stefanie Kremser, Cliff S. Law, Andrew Marriner, Rafel Simó, Birgit Quack, Günther Uher, Huixiang Xie, Xiaobin Xu

OES Faculty Publications

Carbonyl sulfide (OCS) and carbon disulfide (CS₂) are volatile sulfur gases that are naturally formed in seawater and exchanged with the atmosphere. OCS is the most abundant sulfur gas in the atmosphere, and CS₂ is its most important precursor. They have attracted increased interest due to their direct (OCS) or indirect (CS₂ via oxidation to OCS) contribution to the stratospheric sulfate aerosol layer. Furthermore, OCS serves as a proxy to constrain terrestrial CO₂uptake by vegetation. Oceanic emissions of both gases contribute a major part to their atmospheric concentration. Here we present a database of …

Abiotic Formation Of Dissolved Organic Sulfur In Anoxic Sediments Of Santa Barbara Basin, Hussain A. Abdulla, David J. Burdige, Tomoko Komada

OES Faculty Publications

Sulfurization has been found to enhance organic matter preservation and petroleum formation in marine sediments. However, we do not yet have a comprehensive understanding of sulfurization mechanisms. In this study, we investigated several possible mechanisms of dissolved organic sulfur (DOS) formation in the top 4.5 m of anoxic sediments of Santa Barbara Basin (SBB), California Borderland. Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS), we identified chemical formulas of potential dissolved organic matter (DOM) precursors to these DOS compounds. We also examined how the formulas of abiotically formed DOS changed as a function of depth across a major redox …

Temporal And Spatial Scales Of Correlation In Marine Phytoplankton Communities, A. M. Kuhn, S. Dutkiewicz, O. Jahn, Sophie Clayton, T. A. Rynearson, M. R. Mazloff, A. D. Barton

OES Faculty Publications

Ocean circulation shapes marine phytoplankton communities by setting environmental conditions and dispersing organisms. In addition, processes acting on the water column (e.g., heat fluxes and mixing) affect the community structure by modulating environmental variables that determine in situ growth and loss rates. Understanding the scales over which phytoplankton communities vary in time and space is key to elucidate the relative contributions of local processes and ocean circulation on phytoplankton distributions. Using a global ocean ecosystem model, we quantify temporal and spatial correlation scales for phytoplankton phenotypes with diverse functional traits and cell sizes. Through this analysis, we address these questions: …

Biogeochemical Controls Of Surface Ocean Phosphate, Adam C. Martiny, Michael W. Lomas, Weiwei Fu, Philip W. Boyd, Yuh-Ling L. Chen, Gregory A. Cutter, Michael J. Ellwood, Ken Furuya, Fuminori Hasshihama, Jota Kanda, David M. Karl, Taketoshi Kodama, Qian P. Li, Jian Ma, Thierry Moutin, E. Malcolm S. Woodward, J. Keith Moore

OES Faculty Publications

Surface ocean phosphate is commonly below the standard analytical detection limits, leading to an incomplete picture of the global variation and biogeochemical role of phosphate. A global compilation of phosphate measured using high-sensitivity methods revealed several previously unrecognized low-phosphate areas and clear regional differences. Both observational climatologies and Earth system models (ESMs) systematically overestimated surface phosphate. Furthermore, ESMs misrepresented the relationships between phosphate, phytoplankton biomass, and primary productivity. Atmospheric iron input and nitrogen fixation are known important controls on surface phosphate, but model simulations showed that differences in the iron-to-macronutrient ratio in the vertical nutrient supply and surface lateral transport …

The Evolution Of The El Niño-Southern Oscillation And Tropical Pacific Climate Across The Last Deglaciation, Ryan Hunter Glaubke

OES Theses and Dissertations

The El Niño – Southern Oscillation (ENSO) is the largest interannual component of Earth’s climate system, capable of exerting significant influence over global climate patterns that affect communities around the globe. Nevertheless, a comprehensive understanding of the ENSO system and its relationship to tropical Pacific climate dynamics remains unclear. Although new paleoceanographic proxies have shown promise in in their ability to constrain past ENSO change, little is known about how ENSO varied in response to millennial-scale climate events over the last 25,000 years. Here, I present new records of tropical Pacific mean state and ENSO variability over the last 25,000 …

Formation Of Water-Soluble Organic Matter Through Fungal Degradation Of Lignin, Seyyedhadi Khatami, Ying Deng, Ming Tien, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Lignin is a major component of decaying terrestrial vegetation in soils and has been reported to contribute substantially to the formation of soil carbon humus and associated water extracts of soil. To better understand this process of humification, lignin from brown-rot degraded wood is subjected to a white-rot fungus (Phanerochaete chrysosporium)whose enzymes are particularly effective in lignin degradation. This enzymatic attack was monitored by ultrahigh resolution mass spectrometry of water soluble extracts of the fungal cultures. The ensuing molecular level characterizations showed that the P. chrysosporium fungi induced aromatic ring oxidations followed by ring opening as expected. However, …

The Geotraces Intermediate Data Product 2017, Reiner Schlitzer, Robert F. Anderson, Elena Masferrer Dodas, Maeve Lohan, Walter Geibert, Alessandro Tagliabue, Andrew Bowie, Gregory A. Cutter, Peter N. Sedwick, Bettina Sohst

OES Faculty Publications

The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and …

Advances In Amino Acid Analysis For Marine Related Matrices And Its Application To Coastal Shelf Settings In The Canadian Arctic, Rachel M. Mcmahon

OES Theses and Dissertations

Amino acids comprise up to 50% of organic matter in cellular material and are a major fraction of oceanic organic carbon. Amino acids are also considered highly labile during organic matter recycling, making them useful proxies for organic carbon cycling. Nevertheless, analysis of individual amino acids has been burdened by lengthy derivatization and complex analysis since the 1950s. In this thesis, I describe the modification of advanced analytical techniques, developed in the biomedical field, for analysis of marine matrices which allow the determination of at least 40 amino acids without the need for lengthy sample preparation and derivatization, twice the …

Production And Composition Of Pyrogenic Dissolved Organic Matter From A Logical Series Of Laboratory-Generated Chars, Kyle W. Bostick, Andrew R. Zimmerman, Andrew S. Wozniak, Siddhartha Mitra, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Though pyrogenic carbon (pyC) has been assumed to be predominantly stable, degradation and transfers of pyC between various pools have been found to influence its cycling and longevity in the environment. Dissolution via leaching may be the main control on loss processes such as microbial or abiotic oxidation, mineral sorption, or export to aquatic systems. Yet, little is known about the controls on pyrogenic dissolved organic matter (pyDOM) generation or composition. Here, the yield and composition of pyDOM generated through batch leaching of a thermal series of oak and grass biochars, as well as several non-pyrogenic reference materials, was compared …

Evidence For Ephemeral Middle Eocene To Early Oligocene Greenland Glacial Ice And Pan-Arctic Sea Ice, Aradhna Tripati, Dennis Darby

OES Faculty Publications

Earth's modern climate is defined by the presence of ice at both poles, but that ice is now disappearing. Therefore understanding the origin and causes of polar ice stability is more critical than ever. Here we provide novel geochemical data that constrain past dynamics of glacial ice on Greenland and Arctic sea ice. Based on accurate source determinations of individual ice-rafted Fe-oxide grains, we find evidence for episodic glaciation of distinct source regions on Greenland as far-ranging as ~68°N and ~80°N synchronous with ice-rafting from circum-Arctic sources, beginning in the middle Eocene. Glacial intervals broadly coincide with reduced CO_{2 …}

A Near-Global Atmospheric Distribution Of N2o Isotopologues, Peter F. Bernath, Mahdi Yousefi, Eric Buzan, Chris D. Boone

Chemistry & Biochemistry Faculty Publications

The distributions of the four most abundant isotopologues and isotopomers (N₂O, ¹⁵NNO, N¹⁵NO, and NN¹⁸O of nitrous oxide have been measured in the Earth's stratosphere by infrared remote sensing with the Atmospheric Chemistry Experiment (ACE) Fourier transform spectrometer. These satellite observations have provided a near-global picture of N₂O isotopic fractionation. The relative abundances of the heavier species increase with altitude and with latitude in the stratosphere as the air becomes older. The heavy isotopologues are enriched by 20-30% in the upper stratosphere and even more over the poles. These observations are …

Selenium Distribution And Cycling In The Eastern Equatorial Pacific Ocean, Zoe Wambaugh

OES Theses and Dissertations

Oxygen minimum zones in oceanic waters have become increasingly important to the marine environment and society. Low oxygen waters affect not only the distribution and abundance of marine organisms, but also impact the solubility and transport of trace elements that are of biological importance, with the chemical speciation and solubility depending on the actual redox poise of the waters. One redox sensitive trace element of interest is selenium, which can be both toxic and essential for organisms, depending on its chemical speciation. In 2013, the US GEOTRACES program completed the GP16 transect from Peru to Tahiti, going through the oxygen …

Alicyclic And Aromatic Carboxylic Acids In Soil Organic Matter: An Investigation Of Potential Origin And Association With Plutonium Using Advanced Analytical Techniques, Nicole Didonato

Chemistry & Biochemistry Theses & Dissertations

Carboxylic acids are a defining component of soil organic matter, responsible for many of the physical and chemical properties, including metal-organic matter interactions, which govern its role as an important constituent of soils. However, there is a shortage of detailed molecular level information regarding orientation and structural arrangement of carboxylic acids within soil organic matter. This dissertation utilizes electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) as well as solid-state and multi-dimensional nuclear magnetic resonance (NMR) to investigate the molecular formula composition within several organic matter sources and the primary structures that feature carboxylic acids. Soil organic matter …

Dependence Of The Martian Radiation Environment On Atmospheric Depth: Modeling And Measurement, Jingnan Guo, Tony C. Slaba, Cary Zeitlin, Robert F. Wimmer-Schweingruber, Francis F. Badavi, Eckart Böhm, Stephan Böttcher, David E. Brinza, Bent Ehresmann, Donald M. Hassler

Physics Faculty Publications

The energetic particle environment on the Martian surface is influenced by solar and heliospheric modulation and changes in the local atmospheric pressure (or column depth). The Radiation Assessment Detector (RAD) on board the Mars Science Laboratory rover Curiosity on the surface of Mars has been measuring this effect for over four Earth years (about two Martian years). The anticorrelation between the recorded surface Galactic Cosmic Ray-induced dose rates and pressure changes has been investigated by Rafkin et al. (2014) and the long-term solar modulation has also been empirically analyzed and modeled by Guo et al. (2015). This paper employs the …

New And Improved Infra-Red Absorption Cross Sections And Ace-Fts Retrievals Of Carbon Tetrachloride (Ccl4), Jeremy J. Harrison, Christopher D. Boone, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Carbon tetrachloride (CCl₄) is one of the species regulated by the Montreal Protocol on account of its ability to deplete stratospheric ozone. As such, the inconsistency between observations of its abundance and estimated sources and sinks is an important problem requiring urgent attention (Carpenter et al., 2014) [5]. Satellite remote-sensing has a role to play, particularly limb sounders which can provide vertical profiles into the stratosphere and therefore validate stratospheric loss rates in atmospheric models. This work is in two parts. The first describes new and improved high-resolution infra-red absorption cross sections of carbon tetrachloride/dry synthetic air over …

Spatial Patterns Of Sea Level Variability Associated With Natural Internal Climate Modes, Weiqing Han, Gerald A. Meehl, Detlef Stammer, Aixue Hu, Benjamin Hamlington, Jessica Kenigson, Hindumathi Palanisamy, Philip Thompson

OES Faculty Publications

Sea level rise (SLR) can exert significant stress on highly populated coastal societies and low-lying island countries around the world. Because of this, there is huge societal demand for improved decadal predictions and future projections of SLR, particularly on a local scale along coastlines. Regionally, sea level variations can deviate considerably from the global mean due to various geophysical processes. These include changes of ocean circulations, which partially can be attributed to natural, internal modes of variability in the complex Earth's climate system. Anthropogenic influence may also contribute to regional sea level variations. Separating the effects of natural climate modes …

Introducing Global Peat-Specific Temperature And Ph Calibrations Based On Brgdgt Bacterial Lipids, B.D.A. Naafs, G. N. Imglis, Y. Zheng, M. J. Amesbury, H. Biester, R. Bindler, J. Blewett, M. A. Burrows, D. Del Castillo Torres, F. M. Chambers, P. G. Hatcher

Chemistry & Biochemistry Faculty Publications

Glycerol dialkyl glycerol tetraethers (GDGTs) are membrane-spanning lipids from Bacteria and Archaea that are ubiquitous in a range of natural archives and especially abundant in peat. Previous work demonstrated that the distribution of bacterial branched GDGTs (brGDGTs) in mineral soils is correlated to environmental factors such as mean annual air temperature (MAAT) and soil pH. However, the influence of these parameters on brGDGT distributions in peat is largely unknown. Here we investigate the distribution of brGDGTs in 470 samples from 96 peatlands around the world with a broad mean annual air temperature (−8 to 27 °C) and pH (3–8) range …

Community Production Modulates Coral Reef Ph And The Sensitivity Of Ecosystem Calcification To Ocean Acidification, Thomas M. Decarlo, Anne L. Cohen, George T. F. Wong, Fuh-Kwo Shiah, Steven J. Lentz, Kristen A. Davis, Kathryn E. F. Shamberger, Pat Lohmann

OES Faculty Publications

Coral reefs are built of calcium carbonate (CaCO₃) produced biogenically by a diversity of calcifying plants, animals, and microbes. As the ocean warms and acidifies, there is mounting concern that declining calcification rates could shift coral reef CaCO3 budgets from net accretion to net dissolution. We quantified net ecosystem calcification (NEC) and production (NEP) on Dongsha Atoll, northern South China Sea, over a 2 week period that included a transient bleaching event. Peak daytime pH on the wide, shallow reef flat during the nonbleaching period was ~8.5, significantly elevated above that of the surrounding open ocean (~8.0-8.1) as …

Effects Of Nonaerated Circulation Water Velocity On Nutrient Release From Aquaculture Pond Sediments, Xiangju Cheng, Dantong Zhu, Xixi Wang, Deguang Yu, Jun Xie

Civil & Environmental Engineering Faculty Publications

Sustaining good water quality in aquaculture ponds is vital. Without an aerator, the dissolved oxygen in ponds comes primarily from mass transfer at the water-ambient atmosphere interface. As sediment can seriously affect water quality, this study used indoor experiments to examine the nutrient (nitrogen and phosphorus) release mechanisms and fluxes from sediment in aquaculture ponds with moving water but no aeration. The results showed that the ammonia nitrogen (NH₃-N) concentration in the overlying water was inversely proportional to flow velocity and that a higher flow velocity tended to result in a lower concentration in the overlying water, a …

A Tribute To Thomas M. Church: Exploring Chemical Oceanography In The Coastal Zone-The History And Future, Gregory A. Cutter, David J. Burdige

OES Faculty Publications

(First paragraph) One can find different historical perspectives on the development of studying the chemistry of oceans as well as names for this study—marine chemistry, chemistry of the sea, marine aquatic chemistry, marine biogeochemistry, or chemical oceanography. It could be argued that chemical oceanography is the most inclusive for an earth science since oceanography itself is an integrated discipline that links the biology, chemistry, geology, and physics together. Regardless of the name, perhaps the first intensive, modern/post-nineteenth century study of the ocean’s chemistry was the GEOSECS Program from ca. 1970–1978. The significance of GEOSECS was that it examined the chemistry …

Low-Temperature Artificial Maturation Studies Of Type Ii And Type Iii Kerogens: Implications For Biogenic Gas Production, Albert Willy Nguena Kamga

Chemistry & Biochemistry Theses & Dissertations

Ancient organic matter (OM) in shales and coals, known mainly as Type II and Type III OM are known to produce both biogenic, thermogenic gas and oil. In this dissertation, mild artificial maturation, via closed system pyrolysis, is employed to determine the thermal reactivity of Type II and Type III OM beyond diagenesis. We select three Type II kerogens: i) Type II kerogen isolated from recent cores (3.3 Ma, Ro = 0.28) recovered from an upwelling basin in Namibia, Africa referred to as ODP Sediment, ii) Type II-S isolated from sediments (150 Ma, Ro = 0.38) recovered from an outcrop …

The Martian Surface Radiation Environment- A Comparison Of Models And Msl/Rad Measurements, Daniel Matthiä, Bent Ehresmann, Henning Lohf, Jan Köhler, Cary Zeitlin, Jan Appel, John W. Wilson

Mathematics & Statistics Faculty Publications

Context: The Radiation Assessment Detector (RAD) on the Mars Science Laboratory (MSL) has been measuring the radiation environment on the surface of Mars since August 6th 2012. MSL-RAD is the first instrument to provide detailed information about charged and neutral particle spectra and dose rates on the Martian surface, and one of the primary objectives of the RAD investigation is to help improve and validate current radiation transport models.

Aims: Applying different numerical transport models with boundary conditions derived from the MSL-RAD environment the goal of this work was to both provide predictions for the particle spectra and the radiation …